CN110586160A - Preparation method of cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst - Google Patents
Preparation method of cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst Download PDFInfo
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- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 73
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 46
- 239000010439 graphite Substances 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002135 nanosheet Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 239000011593 sulfur Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000047 product Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 10
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 2
- 238000000137 annealing Methods 0.000 claims 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims 2
- 238000005406 washing Methods 0.000 claims 2
- 229910052786 argon Inorganic materials 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 claims 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000004098 Tetracycline Substances 0.000 abstract description 9
- 229960002180 tetracycline Drugs 0.000 abstract description 9
- 229930101283 tetracycline Natural products 0.000 abstract description 9
- 235000019364 tetracycline Nutrition 0.000 abstract description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
- -1 tetracycline compounds Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 150000003522 tetracyclines Chemical class 0.000 description 6
- 239000012467 final product Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention relates to a preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst, belonging to the technical field of photocatalysts. The method prepares the ultrathin graphite-phase carbon nitride nanosheet through twice calcination; ZIF-67 is taken as a template, a sulfur source is introduced, and the obtained product is calcined in an inert gas atmosphere to obtain cage-shaped cobalt sulfide; and coating the graphite phase carbon nitride nanosheet on the surface of the cage-shaped cobalt sulfide to prepare the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst. The composite photocatalyst can efficiently and quickly remove tetracycline compounds in water under visible light, has good stability and catalytic performance, is simple in preparation method, easy to control conditions, low in production cost, green and environment-friendly, and has important significance in photocatalytic degradation of organic pollutants.
Description
Technical Field
The invention relates to a preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst, belonging to the technical field of photocatalysts.
Background
From the perspective of long-term and sustainable development of human society, the development of an environment-friendly and renewable technology capable of solving environmental problems is urgently needed. Among the many proposed strategies, photocatalytic technology has the advantages of economy, safety, sustainability, etc., and is considered to be one of the most effective ways to solve the problem of environmental deterioration. Graphite phase carbon nitride (g-C)3N4) The photocatalyst has the advantages of good physical and chemical stability, excellent photoelectric property, environmental friendliness, correspondence to visible light and the like, and has wide application prospect in the fields of photocatalysis, environmental purification and the like. Although g-C3N4There are many advantages, but its low quantum yield limits its practical application. To this end, researchers have conducted a great deal of research, including band gap tuning, defect control, micro-topography control, surface sensitization, co-catalysts, heterostructures, and the like. Thus, by the pair g-C3N4The modification is carried out to improve the photocatalytic performance of the photocatalyst, and is a great research hotspot in the field of photocatalysis.
Cobalt sulfide (Co)9S8) As a transition metal sulfide, the transition metal sulfide has the characteristics of unique optical property, electrical property, good stability and the like, and is widely applied to the field of catalysis. However, the susceptibility to light corrosion under illumination is a common problem for sulfides, which affects the practical application of cobalt sulfide.
According to the preparation method, the graphite phase carbon nitride nanosheet is coated on the surface of the cobalt sulfide, so that a coat is worn on the cobalt sulfide, and the photo-corrosion can be effectively slowed down. Because the transition metal Co is easy to form a bond with N in the carbon nitride, the transition metal Co and the N can be tightly combined together to form a heterojunction. The cobalt sulfide has unique optical and electrical properties, and can effectively promote the carrier separation of carbon nitride; the carbon nitride is coated on the surface of the cobalt sulfide, and the stability of the cobalt sulfide can be improved. The carbon nitride and the cobalt sulfide are organically combined, and the respective advantages are utilized, so that the photocatalytic performance of the composite photocatalyst is remarkably improved. Therefore, the cobalt sulfide/graphite phase carbon nitride Z-type heterojunction composite photocatalyst designed by the patent has the advantages of low price, easiness in operation, good stability, excellent catalytic performance and the like, and can efficiently and quickly degrade tetracycline compounds in water under the irradiation of visible light. Because the cobalt sulfide/graphite phase carbon nitride composite photocatalyst is not reported in the field of water treatment, the invention firstly provides a preparation method of the cobalt sulfide/graphite phase carbon nitride composite photocatalyst capable of efficiently treating wastewater generated in the processes of pharmacy and the like so as to solve the problem of environmental deterioration.
Disclosure of Invention
The present invention is directed to graphite phase carbon nitride (g-C)3N4) And cobalt sulfide (Co)9S8) The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst is skillfully designed due to respective defects and defects, is used for degrading tetracycline compounds under visible light, and shows great development potential in the field of photocatalytic degradation of organic pollutants.
The invention is realized by the following technical scheme:
a preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst comprises the following steps:
(1) the nitrogen-rich precursor is placed in a crucible with a cover, heated to 450-600 ℃ at the heating rate of 1-10 ℃/min and kept for 3-6 h. After cooling to room temperature, the obtained product is fully ground and transferred to a porcelain boat for calcination at 400-600 ℃ for 1-3 h. The obtained yellow powder is the graphite phase carbon nitride nanosheet.
(2) Cage-like cobalt sulfide (Co)9S8) Obtained by introducing a sulfur source through ZIF-67 as a template and then calcining the mixture in an inert gas atmosphere. The method comprises the following specific steps: cobalt nitrate hexahydrate and 2-methylimidazole (in a molar ratio of 1: 4-8) were dissolved in a methanol solution to obtain two solutions, respectively, and then the two solutions were rapidly mixed together and aged at room temperature for 3-8 hours. The resulting ZIF-67 precipitate was washed several times with ethanol and dispersed in ethanol for further use. An appropriate amount of ZIF-67 was added to an ethanol solution of Thioacetamide (TAA) and stirred to mix well. The mixture was then transferred to a reaction vessel and maintained at 140 ℃ and 200 ℃ for 1-5 h. After cooling to room temperature, the precipitate was washed several times with ethanol and dried to obtain a cobalt sulfide product. Finally, the cobalt sulfide product is placed in an inert gas atmosphere and annealed for 2-8 h at the temperature of 400-600 ℃. The final product is the cage-shaped cobalt sulfide.
(3) Dispersing the obtained graphite phase carbon nitride nanosheet and the cage-shaped cobalt sulfide into methanol, stirring for 10-48 h at room temperature, then placing in an oven, and evaporating the methanol to obtain the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst. Composite photocatalysts with different coating amounts are prepared by controlling the component ratio of the two.
(4) Laboratory simulation: A300W xenon lamp was used to simulate sunlight and fitted with a 400 nm cut-off filter to obtain visible light. With tetracycline (25 mg/L) as a target pollutant, 10 mg of photocatalyst is added into 50 mL of tetracycline solution, and the catalytic performance of the photocatalyst is evaluated by carrying out photodegradation reaction for 60 min under the irradiation of simulated visible light.
The invention has the advantages and effects that:
the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst is prepared, the method has the advantages of simple preparation process, cheap reactants, environmental friendliness and the like, the coating amount of graphite phase carbon nitride is easy to regulate, and the obtained Z-shaped heterojunction has high stability, excellent photocatalytic performance and high degradation capability on tetracycline, and has a great application prospect in the aspect of photocatalytic degradation of organic pollutants.
Drawings
FIG. 1 is an SEM image of a composite photocatalyst cage-shaped cobalt sulfide/graphite phase carbon nitride prepared in example 2;
FIG. 2 is a TEM image of the caged cobalt sulfide/graphite phase carbon nitride composite photocatalyst prepared in example 2.
Detailed Description
Example 1
A preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst comprises the following steps:
(1) the melamine was placed in a crucible with a lid, heated to 500 ℃ at a heating rate of 2.5 ℃/min and held for 5 h. After cooling to room temperature, the product obtained was ground thoroughly and transferred to a porcelain boat and calcined at 500 ℃ for 2 h. The obtained yellow powder is the graphite phase carbon nitride nanosheet.
(2) Cobalt nitrate hexahydrate (175 mg) and 2-methylimidazole (300 mg) were dissolved in 40 mL of a methanol solution, respectively, to obtain two solutions, which were then rapidly mixed together and aged at room temperature for 6 h. The resulting ZIF-67 precipitate was washed several times with ethanol and dispersed in ethanol for further use. An appropriate amount of ZIF-67 was added to 10 mL of an ethanol solution containing Thioacetamide (TAA) and stirred well. The mixture was then transferred to a reaction kettle and held at 180 ℃ for 4 h. After cooling to room temperature, the precipitate was washed several times with ethanol and dried to obtain a cobalt sulfide product. Finally, the cobalt sulfide product is placed in an argon atmosphere and annealed for 8 hours at 500 ℃. The final product is the cage-shaped cobalt sulfide.
(3) Dispersing the obtained graphite phase carbon nitride nanosheet and the cage-shaped cobalt sulfide into methanol, stirring for 24 hours at room temperature, then placing in an oven, and evaporating the methanol to obtain the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst. Composite photocatalysts with different coating amounts are prepared by controlling the component ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets, wherein the mass ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets are respectively 0, 33, 50, 66 and 100 wt%.
(4) Under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 50 wt% has the strongest removal capability on tetracycline within 60 min, and the photocatalytic degradation rate is respectively improved by 2.82 times and 1.22 times compared with that of a cage-shaped cobalt sulfide and graphite-phase carbon nitride single component before compounding.
Example 2
A preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst comprises the following steps:
(1) the melamine was placed in a crucible with a lid, heated to 550 ℃ at a heating rate of 5 ℃/min and held for 4 h. After cooling to room temperature, the product obtained was ground thoroughly and transferred to a porcelain boat and calcined at 500 ℃ for 2 h. The obtained yellow powder is the graphite phase carbon nitride nanosheet.
(2) Cobalt nitrate hexahydrate (175 mg) and 2-methylimidazole (320 mg) were dissolved in 40 mL of a methanol solution, respectively, to obtain two solutions, which were then rapidly mixed together and aged at room temperature for 6 h. The resulting ZIF-67 precipitate was washed several times with ethanol and dispersed in ethanol for further use. An appropriate amount of ZIF-67 was added to 10 mL of Thioacetamide (TAA) in ethanol and stirred well. The mixture was then transferred to a reaction kettle and held at 200 ℃ for 3 h. After cooling to room temperature, the precipitate was washed several times with ethanol and dried to obtain a cobalt sulfide product. Finally, the cobalt sulfide product is placed in an argon atmosphere and annealed for 6 hours at 550 ℃. The final product is the cage-shaped cobalt sulfide.
(3) Dispersing the obtained graphite phase carbon nitride nanosheet and the cage-shaped cobalt sulfide into methanol, stirring for 24 hours at room temperature, then placing in an oven, and evaporating the methanol to obtain the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst. Composite photocatalysts with different coating amounts are prepared by controlling the component ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets, wherein the mass ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets are respectively 0, 33, 50, 66 and 100 wt%.
(4) Under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 50 wt% has the strongest removal capability on tetracycline within 60 min, and the photocatalytic degradation rate is respectively improved by 3.14 times and 1.54 times compared with that of a cage-shaped cobalt sulfide and graphite-phase carbon nitride single component before compounding.
Example 3
A preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst comprises the following steps:
(1) the melamine was placed in a crucible with a lid, heated to 550 ℃ at a heating rate of 10 ℃/min and held for 4 h. After cooling to room temperature, the product obtained was ground thoroughly and transferred to a porcelain boat and calcined at 600 ℃ for 1 h. The obtained yellow powder is the graphite phase carbon nitride nanosheet.
(2) Cobalt nitrate hexahydrate (175 mg) and 2-methylimidazole (350) were dissolved in 40 mL of a methanol solution respectively to obtain two solutions, which were then rapidly mixed together and aged at room temperature for 4 hours. The resulting ZIF-67 precipitate was washed several times with ethanol and dispersed in ethanol for further use. An appropriate amount of ZIF-67 was added to 10 mL of Thioacetamide (TAA) in ethanol and stirred well. The mixture was then transferred to a reaction kettle and held at 180 ℃ for 3 h. After cooling to room temperature, the precipitate was washed several times with ethanol and dried to obtain a cobalt sulfide product. Finally, the cobalt sulfide product is placed in an argon atmosphere and annealed for 6 hours at 500 ℃. The final product is the cage-shaped cobalt sulfide.
(3) Dispersing the obtained graphite phase carbon nitride nanosheet and the cage-shaped cobalt sulfide into methanol, stirring for 24 hours at room temperature, then placing in an oven, and evaporating the methanol to obtain the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst. Composite photocatalysts with different coating amounts are prepared by controlling the component ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets, wherein the mass ratios of the cage-shaped cobalt sulfide and the graphite-phase carbon nitride nanosheets are respectively 0, 33, 50, 66 and 100 wt%.
(4) Under the irradiation of simulated visible light, the composite photocatalyst with the mass ratio of 50 wt% has the strongest removal capability on tetracycline within 60 min, and the photocatalytic degradation rate is respectively improved by 3.02 times and 1.34 times compared with that of a cage-shaped cobalt sulfide and graphite-phase carbon nitride single component before compounding.
Claims (10)
1. A preparation method of a cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst comprises the following process steps:
(1) placing the nitrogen-rich precursor in a crucible with a cover, heating to 450-600 ℃ at the heating rate of 1-10 ℃/min, and keeping for 3-6 h; cooling to room temperature, fully grinding the obtained product, transferring the product into a porcelain boat, and calcining for 1-3 h at the temperature of 400-;
(2) cage-like cobalt sulfide (Co)9S8) The method is obtained by using ZIF-67 as a template and introducing a sulfur source to calcine in an inert gas atmosphere, and comprises the following specific steps: respectively dissolving cobalt nitrate hexahydrate and 2-methylimidazole (the molar ratio is 1: 4-8) in a methanol solution to obtain two solutions, then quickly mixing the two solutions together and ageing at room temperature for 3-8 hours; washing the generated ZIF-67 precipitate with ethanol for several times, and dispersing into ethanol for later use; adding a proper amount of ZIF-67 into an ethanol solution of Thioacetamide (TAA), and stirring to fully and uniformly mix; then transferring the mixture to a reaction kettle, and keeping the mixture at the temperature of 140 ℃ and 200 ℃ for 1-5 h; after cooling to room temperature, washing the precipitate with ethanol for several times and drying to obtain a cobalt sulfide product; finally, placing the cobalt sulfide product in an inert gas atmosphere, and annealing at 400-600 ℃ for 2-8 h;
(3) dispersing the obtained graphite phase carbon nitride nanosheet and the cage-shaped cobalt sulfide into methanol, stirring for 10-48 h at room temperature, then placing in an oven, and evaporating the methanol to obtain the cage-shaped cobalt sulfide/graphite phase carbon nitride composite photocatalyst; composite photocatalysts with different mass percentages (0-100 wt%) are prepared by controlling the component ratio of the two.
2. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: in the step (1), the nitrogen-rich precursor is heated to 450-600 ℃ at the heating rate of 1-10 ℃/min and is kept for 3-6 h.
3. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: in the step (1), the nitrogen-rich precursor can be cyanamide, dicyandiamide, melamine, urea, thiourea or a mixture thereof.
4. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: the temperature is 400-600 ℃ and the calcination time is 1-3 h during the second calcination in the step (1); the obtained yellow powder is the graphite phase carbon nitride nanosheet.
5. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: the molar ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole in the step (2) is 1: 4-8.
6. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: and (3) after the cobalt nitrate hexahydrate and the methanol solution of the 2-methylimidazole are mixed in the step (2), the aging time is 3-8 hours, and the ZIF-67 is fully grown.
7. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: after the sulfur source is introduced in the step (2), the temperature is kept for 1-5h at the temperature of 140-200 ℃.
8. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: in the step (2), the annealing temperature is 400-.
9. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: the inert gas in the step (2) may be nitrogen, argon, or the like.
10. The preparation method of the cage-shaped cobalt sulfide/graphite phase carbon nitride Z-shaped heterojunction composite photocatalyst as claimed in claim 1, which is characterized in that: and (3) stirring and coating the cage-shaped cobalt sulfide and the graphite-phase carbon nitride for 10-48 h.
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